Fused cast refractory



INVENTOR5 ALLEN M ALPER mva Foes/er llfl/Vc/VnLLv 5767M ,4 rra/e/vt' sad- United States Patent 0.

3,140,955 FUSED CAST REFRACTORY Allen M. Alper, Horseheads, and Robert N. McNally, Corning, N.Y., assignors, by mesne assignments, to Cohart Refractories Company, a corporation of Delaware Filed Nov. 24, 1961, Ser. No. 154,754 2 Claims. (Cl. 106-59) This invention relates to magnesia-alumina-chromic oxide fused cast refractory and is particularly concerned with the provision of an improved refractory especially adapted for use in steelmaking furnaces and related apparatus.

Refractory brick for use in steelmaking furnaces, e.g.,

in open hearth furnace roofs, must be able to Withstand a substantial temperature gradient within the brick from the hot face exposed to the furnace interior to the cold outermost face and cyclic temperature changes occurring with the production of each new heat of steel. The refractory brick must also be able to resist the detrimental effects of liquid slags and slag vapors at furnace temperatures. In the present day steelmaking processes utilizing increasingly greater quantities of tonnage oxygen and the resulting higher furnace temperatures, the detrimental effects of temperature gradient, temperature variation and hot slags or hot slag vapors on the refractory are increased to an even greater degree. The primary detrimental effect due to the temperature gradient and the cyclic temperature changes has been found to be spalling of chunks or sections of the brick from the hot face end. The detrimental effect of the hot ferruginous slags or slag vapors has been found to be either a corrosion-erosion wearing away effect on the hot face of the brick or a slag penetration and/ or diffusion into the brick accompanied by an expansion of these slag constituents within the brick structure resulting in portions of the brick bursting off as small chunks or flakes. Over two decades ago, it was proposed to use magnesiaalumina fused cast refractories having at least about 30% MgO for applications in the metallurgical industries where the refractories would have to withstand corrosive conditions. However, these magnesia-alumina refractories generally have been found to possess poor resistance to slag deterioration. Those having lower MgO contents, e.g., 50%, suifer from severe corrosion-erosion effects and. those having higher MgO contents, e.g., 80%, suffer from severe bursting effects. Moreover, these prior magnesia-alumina fused cast refractories generally possess a relatively low modulus of rupture (strength) and they generally have an undesirably high thermal spalling tendency.

Fused cast refractories having an outstanding resistance to slag attack and a high modulus of rupture were subse quently developed. These consisted essentially of MgO, A1 Cr O and iron oxides, e.g., the refractory compositions disclosed in US. Patents 2,599,566 and 2,690,974 to R. I. Magri. However, service experience with these refractories under present day steelmaking practices, e.g., in open hearth furnaces, has shown a less than desirable resistance to thermal spalling.

It has now been discovered that the thermal spalling resistance of these latter fused cast refractories is greatly limited by the relatively large Cr O and FeO contents (the total Fe content being calculated as FeO according to customary practice). Thus, it has been found that a fused cast refractory consisting essentially of a fused mixture of magnesia, alumina, a relatively very small quantity of chromic oxide and the substantial absence of FeO has a greatly improved resistance ot thermal spalling While still possessing a resistance to slag deterioration and a 3,140,955 Patented July 14, 1964 modulus of rupture greatly superior to the early magnesia alumina fused cast refractories.

Accordingly, it is an object of this invention to provide a new magnesia-alumina-chromic oxide fused cast refractory having an improved combination of properties comprising good modulus of rupture, good resistance to slag deterioration and outstanding resistance to thermal spalling.

In the drawing, FIGURES 1 through 5 illustrate a scheme of spalling defect classification for thermally cycled brick.

The improved fused cast refractory of this invention consists essentially of, by weight, the following on an oxide basis:

Broad, Preferred, percent percent 56-85 60-75 13-4 25-35 MgO dz A120 at least at least 92 O zOa 0. 4-4. 5 0. 7-4 FeO up to 3.5 up to 2.5 CaO up t03 up to 2 Si02 up to 3 up to 2 B203 up to 0.5 up to 0. 2

1 The total Fe content being calculated as FeO according to customary practice.

7 While it is desirable to make the fused cast refractory of the invention substantially all MgO, A1 0 and Cr O for an optimum combination of properties, it is not economically desirable because of the greater expense involved for pure oxide raw materials, particularly chromic oxide. Hence, less pure and less expensive raw materials can be utilized which provide no more than the above-stated limited quantities of optional constituents, i.e., FeO, CaO, Si0 and B 0 and very minor impurities. Excessive quantities of FeO and B 0 materially decrease the resistance to thermal spalling and excessive quantities of CaO and SiO materially decrease the resistance to slag corrosion-erosion.

In the production of the refractory of this invention, raw materials of suitable purity are proportioned in accordance with the desired final composition and are preferably premixed prior to charging into the melting furnace. The batch material is then processed according to the well-known fusion casting techniques, for example, as disclosed in United States Patent 1,615,750 to G. S. Fulcher.

Examples of raw materials used and found suitable are shown below in terms of typical chemical analyses in weight percent:

' Calcined Alumina Transvaal Maguesite Chrome Ore 98.0% MgO 99.2% A1 03 44% CD03 1. OaO 0.02% SiO; 23% FeO 0.4% SiOz 0.03% F0203 13% A1203 0 2% F6203 0.45% N320 12% MgO 0 2% A1203 0.41% Ignition 4% SiO;

oss.

0.5% Ignition 0.5% CaO Loss.

9 e3 refractory samples in a molten slag composed of 80% Fe O and 20% CaMgSiO (Monticellite slag) at 1650 C. for 48 hours. The percent change in dimension is The classification values in Table II are the average of the four bricks of each composition.

measured /2 below the slag line by comparison of the Table H tested specimen dimension with the known original dimension prior to testing. Correlation of these test results with 5 Castmg N 15 16 17 18 19 similar compositions tested in actual furnace service have M O t t g n 4 shown that refractory l fe becomes intolerably short gi 2 gig gag 338 when a refractory compos1t1on exhibits a bursting expan- (3:203, wt. percent 3.0 2.3 4 8.8 sion (plus percent value) in excess of 8% or corrosion- 0 53% 3:2 3:: 8:% erosion (minus percent value) in excess of about 30%. SlO2, Wt.DC!'C0l1l3 7 ,2 The ideal resistance to slag deterioration would be Spaumg Classification rated 0%.

Table I CastingNo 1 2 3 4 5 0 7 8 i 9 I 10 11 i 12 13 I 14 MgO,wt.percent..- 78.4 07.7 04.7 s4 80 70.7 74 07 55.7 02.4 78.4 08.6 03.7 53.9 A1203, wt. percent- 18.0 28.9 29.9 13 15 18.8 22 29 30.8 32.2 20.9 34.0 40.8 Cr O ,wt.percent. 2 2 4 0.86 2.5 0.43 1.0 1.0 2.4 2 4 FeO wt. percent. 02 02 0 2 0. 43 1.2 0.2 0.8 0.8 1.2 2.5 0.2 02 0.2 0.2 CaO,wt.percent 0.8 0.7 0 7 0.5 0.6 0.5 0.5 0.5 0.5 0.5 0.8 0.7 0.7 0.0 SiOz,Wl;.pe1CGlll; 0.3 0.3 0.3 003 0.4 0.2 0.2 0.2 0.2 0.2 0.3 0.3 0.3 0.2 Slag Deterioration,

p r 5 +5 +2 +5 +4 +0 +2 +30 Modulus of Rupture,

psi 2,200 3,400 4,100 1,200 1,800 3,600 1,700 3,100 4,400 1,000 1,800 3,100 3,650

B The total Fe content is included and calculated as being FeO.

Table clearly illustrates the good resistance to lag Thus, it can be seen that the refractory of the present deteroratlon F2 g a z l d mventloil- Thls 30 invention provides good resistance to slag deterioration can e.most slgn} can y 1 us m e y companpg and good modulus of rupture with concomitant high reples W1th and Without Cr O but W1th substantially the Si t t th 1 f same ratio of MgO:Al O e.g., Casting Nos. 6 and 11, S ance 0 Sp l ng a com matlon Propertles 2 and 12, 10 and A comparison of these Same heretofore unobtarnable 1n fused cast refractones for servl l shows h d d l f rupture f h 35 ice in steelmaking furnaces, such as the electric-arc meltrefractory of the present invention. Moreover, Casting ing furnaces and the roofs of open hearth furnaces. How- 14 illustrat the effect of a 8 Content ever, the utility of the invention refractory is not neces- Whereby the resltance to slag i i very sarily restricted to the aforementioned applications, but poor h Flaxlmum M Content 0 t e Invention can be used in other applications where deemed desirable, fractory 1s dictated by virtue of the fact that the melting 40 f 7 1e t kl d th u t m point becomes too high above 85% MgO to obtain proper or 6 Cemen Ins an m e S pet's rue re melting and casting of glass melting tank furnaces.

The high degree of resistance to thermal spalling of the It should be understood that the illustrated embodiinvention refractories can be seen by reference to Table ments f h invention may b i d ithi th irit C es 15: and 17 are examples 01 the Pres of the invention, and, accordingly, it is intended that the mventlpn and Castmg N 18 and 12 a repr.esentascope of the present invention be limited only by the two of pr1or art refractones. The spalllng resistance d d 1 s classification is based on an accelerated test simulating appen e c the characteristic thermal gradient and cyclic thermal What Is clalmed changes that occur in steelmaking furnace refractories. A fused Cast refractory COHSlStlng essentlally y The test consists of heating a panel of four 3" x 4 /2 x weight, 56% to 85% MgO, 13% to 40% A1 0 the 13 bricks of each composition to 1250 C., then sub- Sum f l A1 0 b i t l t 90%, 0,4% t ect mg the bucks to a programmed thermal cycle con- 45% crzos, up to 35% F60, up to 3% cao, up to 3% sisting of: 2 hours hold at 1250 C., 2 hours heating up Sio and up to 0 5% B O to 1650 c., 2 hours hold at 1650 c., 2 hours cooling 2 2 to 12500 C and repeating this cycle an additional 59 2. A fused cast refractory conslstlng essentially of, by

9 times for a total of 60 cycles. At the end of 60 cycles, Welght, 60% to 8 25% to 35% A1203 the Sum the bricks are cooled to room temperature and classified of MgO plus A1 0 being at least 92%, 0.7% to 4% in accordance with the following scheme: Cr O up 2.5% FeO, up to 2% C210, up to 2% SiO and 60 up to 0.2% B 0 Defect Type of Defect Typical Class Appearance References Cited in the file of this patent NQ mph d d k UNITED STATES PATENTS l l r i e siir lii i fz iri 21 1 31 oii g crzcks FIGURE 3: 5 2,062,962 Baumann et a1. D86. 1, 1936 SW11 crack gggggg; 2,235,077 McMullen Mar. 18, 1941 Loose spall UNITED STATES PATENT GFFICE @ERT-IFICATE OF CORRECTION Patent No. 3 140,955 July l l 1964 Allen M. Alper et a1 It is hereby certified that error appears in the above numbered patent requiring correction and that the. said Letters Patent should read as corrected below.

In the grant, lines 3 and 13, and in the heading to the printed specification line 5, for "Cohart Refractories Company"' each occurrence read Corhart Refractories Company column 1, line 70, for "0t" read to column 4. Table ll in the heading to the last column thereof for "19" read 12 Signed and sealed this 29th day of December 1964,

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER At tcsting Officer Commissioner of Patents 

1. A FUSED CAST REFRACTORY CONSISTING ESSENTIALLY OF, BY WEIGHT, 56% TO 85% MGO, 13% TO 40% AL2O3, THE SUM OF MGO PLUS AL2O3 BEING AT LEAST 90%, 0.4% TO 4.5% CR2O3, UP TO 3.5% FEO, UP TO 3% CAO, UP TO 3% SIO2 AND UP TO 0.5% B2O3. 